Article having applied to the surface thereof, an anti-fouling composition comprising a polymer and an organo-tin compound

ABSTRACT

WHEREIN R1 is n-dodecyl and R2 and R3 are methyl.   In an article to be used in or under water and in constant contact with the water, at least the surface of the article is composed of an anti-fouling composition which comprises a polymer and an organo tin compound of the formula:

liftwlfiielil ARTICLE HAVING APPLIED TO THE SURFACE THEREOF, AN ANTI-FOULING COMPOSITION COMPRISING A POLYMER AND AN ORGANO-TIN COMPOUND Inventors: Mitsuo Onozuka; Yasuo Hayashi;

Yoshiaki Adachi, all of lwaki, Japan Kureha Kagaltu Kogyo Kabushiki Kaisha, Tokyo, Japan Filed: Apr. 27, 1972 Appl. No.: 248,270

[73] Assignee: A

Foreign Application Priority Data Apr. 27, 1971 Japan 4627158 Nov, 1, 1971 Japan 46-86263 Dec. 27, 1971 Japan 46-10548 US. Cl.... 117/1385, 106/15 AF, 117/1388 E, 260/4575 K, 260/429.7, 424/288 Int. Cl B32b 27/06 Field of Search 117/1388 E, 138.5; 106/15 AF; 260/4297, 45.75 K; 424/288 References Cited UNITED STATES PATENTS 10/1960 Leatherland 117/1385 2/1961 Sparmann 106/15 8/1963 Gelbert 260/4297 8/1965 Santo 260/4297 OTHER PUBLICATIONS Organic Metallic Compounds, Vol. 11, 2nd Ed. Springer-Verlag, New York Inc., OD 411 D9, 1966.

Primary Examiner-William D. Martin Assistant Examiner-Sadie L. Childs Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT In an article to'be used in or under water and in constant contact with the water, at least the surface of the article is composed of an anti-fouling composition QR Ila/ 15533111" which comprises a polymer and an organo tin compound of the formula:

1 R1 Tn wherein R is n-dodecyl and R and R are methyl.

11 Claims, N0 Drawings x, z a ay:

ARTICLE HAVING APPLIED TO THE SURFACE THEREOF, AN ANTI-FOULING COMPOSITION COMPRISING A POLYMER AND AN ORGANO-TIN COMPOUND BACKGROUND OF THE INVENTION Field of the Invention This invention relates to a process for attaining antifouling of a constantly water-contacting surface of an article against deposition of water micro-organisms by the use of organo-tin compounds. It relates also to an article capable of providing such anti-fouling characteristic.

As the articles of the above kind, fishing and fishcultivating nets, floats, boat hulls, fishery tools, ropes and the like can be mentioned.

When water micro-organisms such as barnacle, serpula, polyzoan, mussel, ascidian, laver, green laver and- /or the like are attached onto the surface of a waterimmersed article and grow thereover, the mechanical strength as well as the durable life of the article may be substantially reduced, as is very well known, In addition, especially in the case of fishing nets, the fluid resistance to water flowing through the meshes of the net becomes larger and larger, whereby in the case of fish cultivation in a limited area of the sea, for instance, in an area surrounded by such a net, the fish under cultivation are adversely affected by a poor supply of oxygen dissolved in the water. In the case of a fishing net, the increased flow resistance gives rise to substantially increased man power needs for the fishery.

In order to minimize these drawbacks, fishing nets and the like articles floating on or immersed in the water must be frequently dried under daylight so as to kill the deposited and flourishing water microorganisms, thus causing a large amount of additional man power to be consumed for this purpose and substantial mechanical damage of the net. These are sincere and grave troubles to the fishermen.

In the case of the culture of oysters and the like shellfish, the deposit of water micro-organisms on the suspension ropes and floats of the culturing net will invite an increased weight thereof and'the dipping depth of the suspended culture net will be correspondingly increased, which adversely affects the growth of the oysters. In the case of the fixed fishing net, the same cause as above referred to will reduce the yield ofcaught fish.

In order to avoid these conventional drawbacks, it has already been proposed to use inorganic anti-fouling agents such as cuprous oxide, mercury oxide or the like; organocopper salts such as copper naphthenate, copper oleate or the like; organo-tin compound such as bis-tributyl tin oxide, independentlyor in combination,

so as to prevent deposition of water micro-organisms on the articles exposed to sea or river water. These substances are highly poisonous and known especially as effective agents of ship bottom anti-fouling paint. With use of these anti-fouling substances, various disadvantages have been encountered. As an example, the material of the articles to be protected has been found substantially deteriorated or damaged by the aggression of these agents per se, or of the modified substances therefrom in the presence of industrial fouling substances dissolved in the water. A further considerable disadvantage derived from the use of these conventional anti-fouling agents is such that these can be applied only through a coating technique. Especially, a

uniform coating of these substances is highly difficult. In addition thereto with the use of the developer as employed in the coating application of these anti-fouling agents, it has been frequently encountered that the developer is rather liable to dissolve into the water and the anti-fouling agent may frequently be sealed off from the applied article surface. On the other hand, when the developer is difficult to dissolve, the waterimmersed article such as fishing net and fishery rope, is liable to become stiffened and the anti-fouling agent has frequently be sealed off within an unexpectedly short period.

SUMMARY OF THE INVENTION It is the main object of the present invention to provide a process for preventing the fouling of articles exposed to water (hereafter often referred to as antifouling of water-exposed articles) in an efficient and durable way, so as to suppress the deposition of water micro-organisms thereon, and an article having its entire surface effectively protected in this manner.

A subsidiary object is to provide a process and an article of the above kind, whereby no deterioration ofthe article material is substantially invited.

A further subsidiary object is to provide a process and an article of the above kind, whereby which substantially no poisonous effect is provided not only upon the treating personnel, but also upon fishes living in the water.

for fulfilment of these objects, it is proposed by the present invention to use an organo-tin anti-fouling agent having a trialkyl tin radical, one of the three alkyl radicals coupled with the tin being C -C an alkyl radical. This kind of organo-tin anti-fouling agent has a substantially low soubility in water, and thus dissolves in the water onlysparingly. Therefore, the agent does not readily lose its initial concentration on the articles surface, when it is applied thereto by coating or blending, as will become more clear as the description proceeds, whereby its effectiveness is guaranteed for an extended time period.

By the very presence of the higher alkyl radical in the molecular structure of the anti-fouling agent, a proper mutual solubility is obtained with a synthetic resin material when the latter is used as the material of the article to be protected in the water, thereby providing convenience and advantages when the anti-fouling agent is used through blending, so as to provide an evenly comixed blend.

The improved trialkyl tin compound used as the antifouling agent has a satisfactory thermal stability over conventional trialkyl tin compounds of lower alkyls, without fear of loss of effectiveness even through blending at an elevated temperature.

When the article is manufactured from such a blended material, it has been observed that the antifouling agent will bleed out from the interior towards the surface of the article, whereby the anti-fouling ef feet is supplemented with lapse of time and is maintained for a prolonged period.

The superior blending characteristics of the antifouling agent with a synthetic resin, or more specifically, the improved thermal stability, mutual solubility and bleedahility, can be still further improved by proper selection of the anionic substituent radical of the anti-fouling, organo-tin trialkyl compound.

in place of blending the organo-tin trialky compound, a mixture of the compound with a synthetic resin may be dissolved or suspended in a solvent and the solution or suspension can be applied by coating.

The application of the organo-tin trialkyl compound proposed by the invention to a synthetic resin to protect the article made of the resin, through either blending or coating, does not deteriorate the stability of the resin and various other advantageous physical properties thereof.

As an example, when the anti-fouling agent consisting of dimetltyl-n-dodecyl tin stearatc having such molecular structure:

lZ ZS CH3 O c ir ss ll 0 CH3 is blended with vinylidene chloride/vinyl chloride copolymer (Krehalon") and the blended material is fabricated into fishing nets and like articles exposed to water, the following results have been obtained as tabulated in Table 1.

As ascertained by thin layer chromatography or IR- spectrum analysis the anti-fouling agent consisting of the above stearate showed practically no deterioration during the blending process. This effect was ascertained by the said testing procedures by observing compound which had bled onto the article surface.

Table l-(ontinucd DEP (diethyl phthalate) 2 PHR alpha-MBE (dimethyl benzyl ether) 3 do. barium stearatc 0.5 do. carbon black 0.065 do Remarks 2: spinning conditions spinning unit (model: BeckZ) nozzle. single orifice. 2 mm dia. extrusion rate l4 g/min; L000 denier. stretch 3 times internal temp. l70"C Remarks 3:

Thermo-stability tests were carried out on a press and with use of the above compounding mixture. excluding the carbon black.

As for the toxicity, several tests were made with the use of. as an example, bis-(dimethyl-n-dodecyl tin)oxide and dimethyl-n-dodecyl tin stearate, which were compared with a conventional butyl tin compound. In these tests, the compound was coated on a polyethylene fishing net and a Krehalon resin net for carrying out tests on living fishes. The results are shown in the following Table 2.

From these comparative tests, it will be seen that the Table 1 toxicity of the above improved compounds upon living h d. h d d I fishes is lower than the comparative conventional antiwit no tmet yno ecy tested material organic antitin stearate fouhng agents fouling agent i PHR 2 PH As a further example, acute toxicity was tested by added oral administration of the compound mice. LD was tensile strength 1.53 157 1,4 0.88 g/ltg and thus highly safety in comparison with (E/d) LD 0.2 g/kg of conventionally known bts-(trt-n-butyl elongation 26.4 30.8 27.0 t. .d

percentage in OX1 6.

Table 2 Toxicity Tests of Fishing Nets Coated with Organo-tin Anti-fouling Agents Number l 2 3 4 organo-tin anti-fouling bis-(dimethyldimethyl'nbis-(tri-ntri-n-butyl agent n-dodecyl tin) dodecyl tin butyl tin) tin stearate oxide stearate oxide containing percentage 5 wt. 5 wt. 5 wt. 7v 5 wt. mixing rate of developer 5 wt. 5 wt. 71 5 wt. 70 5 wt. 70 "Elbaxit) added quantity of wt. (70 90 wt. 90 wt. 90. wt. 70 solvent naphtha weight of fishing 7.84 8.00 7.98 7.87 net. g polytotal deposition cthylquantity of antiene fouling agent and 4.3 3.7 3.4 3.7 fishdeveloper relative ing to the weight of net net.

weight of net. g 7.87 7.69 7.89 7.87 "Kretotal deposition halquantity of antion"- fouling agent and 1.6 L6 1 6 l 5 fishdeveloper relative ing to the weight of net net. 70

no mortality time for complete 44 (even after 20 44 mortality, hrs. lapse of 480 hours) Remarks. l.'l'he area of net coated 10cm x 10cm 2. "Elliott-40" consists of ethylene (b0 wt.71 )/vinyl acetate (40 wt. '7: copolymcr (melt index 1 255) 3. The used vessel is a steel vat. enameled. 30 cm Mia.) X 30 cm (height) 4. Test measure: four vessels were filled with water and left to rest for 24 hours. Then, l0 goldfish having a mean body weight of 4.0 g, mean length: 6.0 cm were introduced in each of these vats. Then. these fish were left alone for 24 hours and then two fishing nets having the size given above and being coated with the anti-fouling agent on the polyethylene of the nets were introduced into each of the vats and the mortality observed for the necessary time period. za 5. Water temperature 20C.'Water quantity 30 lit.lvat. t

Based upon the aforementioned objects, and experimental results, the process features of the present invention reside in a method for the prevention of fouling of an article by deposition of water micro-organisms by application of a composition comprising an organo-tin compound of the general formula:

wherein R stands for a higher alkyl group of (T -C R or R stands for a lower alkyl group of C,C the total number of alkyl carbons of R,, R and R being less than X stands for a group of having the same meaning as before for R R and R halogen, alkoxyl-, thio-alkoxyl-, and organic acid radical or a surfactant radical exclusive of active hydrogen, ammonium or metallic radical.

The improved trialkyl tin compound as is used in the present invention has a higher alkyl radical of C C as was referred to above. I

Such alkyl may preferably be noctyl, 2-ethylhexyl, n-decyl or n-dodecyl. The remaining two of the three alkyls are C,-C lower alkyl. As the lower alkyl, these may be same as or different from each other and can be methyl, ethyl, n-propyl, i-propyl. The total number of the carbon atoms in the alkyls (three) should preferably be less than 15, inclusive.

The anionic substituent radical (with exception of the case of bis-(trialkyl tin)oxide may be halogen, preferably chlorine, bromine or iodine.

In this case of X being an alkoxy radical, it may be an alcoholic residual radical of mono-, dior trivalency. it may be among others derived from the following alcohol groups saturated and unsaturated, straight chain or branched aliphatic alcohols, saturated and unsaturated cyclo-aliphatic alcohols and aromatic alcohols such as: methyl alcohol; ethyl alcohol; n-propyl alcohol; i propyl alcohol; n-butyl alcohol; sec.-butylalcohol; i-butyl alcohol; tbutyl alcohol; n-amyl alcohol; I- amyl alcohol; 2-ethyl-l-butanol; neopentyl alcohol; diethylcarbinol; Z-pentanol; methyl isopropyl carbinol; t-amyl alcohol; n-hexyl alcohol; dimethyl isopropyl carbinol; n-heptyl alcohol; n-octyl alcohol; n-decyl alcohol; n-dodecyl alcohol; myristyl alcohol; hexadecanol; n-octadecanol; allyl alcohol; crotyl alcohol; methyl vinyl carbinol; allyl carbinol; methylpropenyl carbinol; 4-pentene-2-ol; IO-undecen-l-ol; propagyl alcohol; 2- butyne-lol; 2-pentyne-l-ol; l,4-pentadiene-3-ol; ethyl-cello-solve; butyl-cello-solve; ethylene glycol; propylene glycol; propylene glycol; ethylene glycol; 2-methyl-l,2-propanediol; trimethylene glycol; 2,4- pentanediol; hexamethyltrimethylene glycol; tetramethylene glycol; 1,4-hexanediol; 3-butene-l,2-diol; 2,5-dimethyl-3'hexene-2,5-diol; Zbutene-IA-diol; glycerin; 1,2,3-pentanetriol; Z-methyl-l ,2,3- propanetriol; 2-methyl-2,3,4-butanetriol; phenol; cresol; xylenol; propylephenol; butylphenol; catechol; resorcin; urushiol; guaiacol; eugenol; pyrogallol; cyclopropanol; cyclopropylethylene glycol; cyclobutyl methylcarbinol; cyclohexanol; 1,3-cyclohexanol; l,3- cyclohexanediol; l-cyclohexenol; benzyl alcohol; naphthol and the like.

X, when thioalkoxyl, C C may be selected from the following group of thioalcohols (mercaptans) giving a thioalcoholic radical of mono-, di-, or trivalency,

such as:

methylmercaptan, ethyl mercaptan, npropylmercaptan; i-propylmercaptan; nbutylmercaptan; i-butylrnercaptan;. tbutylmercaptan; n-amylmercaptan iamylmercaptan; n-hexylmercaptan; noctylmercaptan; 2-ethylmercaptan; ndecylmercaptan; n-dodecylmercaptan; n-hexadecylmercaptan; neopentylmercaptan; allylmercaptan; 3-N,N-diethylaminopropylmercaptan; 1,2- dithioglycerol; 2,2-dimercaptopropane; 1,1-dimercaptocyclohexane; thiophenol; o-mercaptobenzoate; o-chlorothiophenol; m-bromothiophenol; pthiocresol; ethyl-beta-mercaptocinnamate; alpha-mercaptothiophene; thioacetic acid; dithioacetic acid; beta-mercaptopropionic acid and the like.

Thus, it will be seen the thioalcoholic radical may be derived from straight chain or branched aliphatic thioalcohol or saturated or unsaturated cycloaliphatic thioalcohols.

X, when an organic acid radical, may be preferably derived from organic acids, C C of mono, dior tribasic character; such as acetic acid; propionic acid; butyric acid; valerianic acid; caproic acid; pelargonic acid; caprinic acid; n-undecylenic acid; myristic acid; palmitic acid; lauric acid; margarine acid; stearic acid; behenic acid; metacrylic acid; lignoceric acid; vinyl acetic acid; tiglic acid; 4-pentenic acid; alphaethlcrotonic acid; 2-octenoic acid; 4-dodecenic acid; propiolic acid; 9-undecenoic acid; stearolic acid; 2,4-pentadienic acid; linileic acid; linolenic acid; malonic acid; succinic acid; adipic acid; dodecanedicarboxylic acid; maleic acid; fumaric acid; itaconic acid; benzoic acid; toluylic acid; phthalic acid; cinnenic acid; alphaallylphenylacetic acid; alpha-benzylacrylic acid; alpha-naphthic acid; naphthalene-1,2-dicarboxylic acid; naphthalic acid; cyclopropanecarboxylic acid; l-cyclohexenecarboxylic acid; 1- phenylcyclohexane carboxylic acid and the like.

Therefore, it will be seen that the acid under consideration may be preferably selected from saturated and unsaturated aliphatic carboxylic acids; cycloaliphatic carboxylic acids and aromatic carboxylic acids.

The main skeleton of each of these alkoxyl radicals, thioalkoxyl radicals and organic acid radicals may have a branched substituent such as:

halogen; alkoxyl-, amino-, thioalkoxyl-, carbnyl-, or

carboxylic acid radical.

As the surfactant for providing a surfactant radical may have a functional radical comprising at least an active hydrogen, such as 'NH -NHR; OH; -SH; COOH or the like, said active hydrogen being occasionally substituted by a metallic or ammonium atom. The surfactant may have at least one of such radicals in its molecule. This surfactant may be a commercially available anti-static agent adapted for blending.

Certain of these may be:

R- N R' cooM,

thane resin; epoxy resin; phenolic resin or the like.

As an example, 100 parts of the resin are mixed preferably with 0.5 200 wt. parts of the organo-tin compound.

When the article having a water exposed surface is a melt-spun fibrous material, the latter must naturally be of a thermoplastic nature. In this case, 0.5 wt. parts of the trialkyl tin compounds may preferably be blended therewith.

When the anti-fouling substance is applied through the coating technique, the organo-tin compound in a solution is preferably used. The cooperating resin may be an ethylene/vinyl acetate copolymer, including wt. of vinyl acetate component and having a melt index, ASTM D 1238 of 2 400 g/lO min.

N- CH2 N- CH R R'- C N CH N CH2 2 HO CH CH OH R'COOM CH COOM R- CO'O (CH CH O if" M CH O); M,

R- O- CH CH -CHOM The synthetic resin to be admixed or blended with the organ-tin compound employable in this invention may be:

ethylene; propylene; vinyl chloride; vinylidene chloride; vinyl fluroride; vinylidene fluoride; vinyl acetate; acrylonitrile; (metal) acrylic acid esters; a polymer and/or copolymer of styrene, butadiene or the like, polyamide resin polyester resin; polyure- It may be polyvinyl chloride; vinylidene/vinyl chloride copolymer; polyamide resin; polyethylene; polypropyrene; polyester; polyvinyl acetate acrylonitrileI- styrene/butadiene copolymer, or the like.

The solvent is preferably selected from the following group:

acetoaldehyde; acetone; ethyl acetate; propyl acetate; benzene; toluene; xylene; cyclohexane; cyclohcxcne; tctrahydrofuran; heptane; hexane; kerosene; solvent naphtha; gasoline; tetrachloroethylene; trichloroethylene or the like.

The organo-tin compound, 1-20 wt. and resin, 2-20 wt.%, may be dissolved or suspended in the solvent and applied to the article by any conventional coating method.

MANUFACTURING EXAMPLE 1 Manufacture of trimethyl-n-dodecyl tin Grignard reagent comprising methyl iodide 1727.8 g

and metallic magnesium 325.6 g was reacted in nbutyl ether equivolumetric to the methyl iodide, with a solution of n-dodecyl tin trichloride, 1280 g, in n-butyl ether at 30C of reaction temperature, and conventionally after-treated. The formed organic phase was distilled to trimethyl-n-dodecyl tin, 761 g. Yield: 70.4% based upon the charged ndodecyl tin trichloride.

110-114C/0.75 mm Hg; 1.4620.

MANUFACTURING EXAMPLE 2 octyl tin.

I 6 11 n-C H |Sn b.p. l110C/0.4 mm Hg; n 1.5020

MANUFACTURING EXAMPLE 3 Manufacture of bis-(dimethyl-n-dodecyl tin)oxide Dimethyl-n-dodecyl tin iodide (compound in Example to follow), 869 g, was dissolved in benzene, 6 lit., and added with a wt caustic soda solution including caustic soda, 117 g., said mixture being subjected to hydrolysis at 3040C Upon completion of the reaction, the benzene phase was separated and the benzene phase was distilled off. The solid residual was added to acetone and refined through recrystallization to bis-(dimethylm-dodecyl tinloxidc. 411.9 g.

Yield: 64.7% based upon the introduced dimethyl-n- I 10 40-42(.; white powder;

MANUFACTURING EXAMPLE 4 mp. state Manufacture of dimethyln-dodecyl tin stearate (see I of distilled water in a water separator attributed thereto, it was adjudged that the reaction had progressed substantially stoichiometrically.

Upon termination of the reaction, toluene was distilled off and the residual white solid product was found to be dimethyl-n-dodecyl tin stearate, 690 g.

mp. 50C.

MANUFACTURING EXAMPLE 5 Manufacture of dimethyl-n-dodecyl hydroxyethyl-2-undecyl-2-carboxymethyl-2- imidazolinium hydroxide (refer also to Example 45 to follow) Dimethyl-n-dodecyl tin chloride, 35.4 g, and sodium- 1-hydroxyethyl-2-undecyl-2-carboxymethyl-2- imidazolinium hydroxide. 36.7 g, were added to toluene, ml, and the mixture was brought into reaction for 3 hours under refluxing conditions. The formed sodium chloride was filtered off. Toluene was distilled off from the organic phase and white yellow paste, 66 g. The separated sodium chloride weighed 5.5 g in its dried weight. The yield of the effective substance amounted to 94% upon consideration of the above.

In the following, the invention will be demonstrated more specifically by way of a number of Examples.

tin-l- EXAMPLES 1-5 in the following way.

The compound under test was dissolved in benzene and the concentration was properly adjusted to remain uniform at 0.0003 mole of the compound per cm by coating administration thereof with a painting brush on a smooth square plate (5 X 20 X 1 cm) prepared from a Japanese oak tree and thereupon dried. The thus coated plate was immersed in the the sea water to a depth of 1.5 m.

The co-kneadability in the above sense was measured in the following way.

A mass of polyethylene (Sholex 6006C", manufac tured and sold by a Japanese chemical firm, SHOWA DENKO KABUSHIKI KAISHA, Kawasaki, Japan) was admixed with the antifouling agent in ratios of 2 and 4 PHR, respectively, and compounded at 150C for 3 minutes by calendering. During this mixing operation,

11 the co-miscibility of the antifouling agent and the kneadability of the compound were measured.

The bleedability of the antit"ouling agent on the surface of a polyethylene solid sheet by pressing the compound at 250C for or minutes, respectively, was

TABLE 3 Total Physical constants Anti-fouling perfor- Conumber of mance kneadability carbons Ref. index mt p. C After one After three :1 month months bis-(dimethyl-n-octyl tin)oxide 1 B l'I 10 1.4816 0 0 Good CH ?Sn-O CH3 WW 2 bis-(diethyl-n-octyl tin)oxide 2 s n 12 1. 4853 o I o pounds in CZH Sn O Examples Z S Z biu-(dimethyln-decyl tin)oxide 3 IO ZI 12 81-82 0 0 Best CH Sn 0 bis-(di-n-propyl-n-octyl tin)ox:lde

H C3 7 2 Combis-(dimethyl-n-dodecyl tin)oxide pounds H in Ex- 5 12 25 14 -42 0 0 Best amPles CH fi 3 2 bis-(dimethyl-n-hexyl tin)oxide l 6 t3 a 1. 4855 o A Bad ctr fisn 0 CH3 2 biS-(tri-n-butyl tin oxide H M". V- Refer- H ences 2 4 9 12 O A n O C HQ/Sn 4 9 2 bis-(diethyl-n-dodecyl tin)oxida 3 lZ ZS 14 1.4863 c X Good H 5 C2 n 0 Refer- Z 5 Z ences bis-(dimethyl-n-tetradecyl tin)oxide 4 I4 Z9 16 1. 4840 A x CHi/Sn 0 CH3 Remarks: Degree of fouling is expressed as follows:

A small quantity of deposited water micro-organisms observed;

also observed. The bleedability was also observed visually upon lapse ofa week at normal temperature on the same polyethylene solid sheet or panel. The bleedability as listed in the following was determined from a general consideration of these tests.

As reference, tributyl tin and dimethyl-n-hexyl tin compounds were used. By use of these known compractically no deposition of water micro-organisms X 2 overall and substantial deposition observed.

By these Examples, it is shown that the trialkyl tin compounds having different kinds of alkyls show almost unchanged anti-fouling capabilities even when the negative substituent radicals are replaced by other radicals. Even if the capabilities should be changed, this is only slightly caused by the altered physical constants.

The fouling tests were executed as before.

TABLE 4 Molecular structure of organo-tin compound or anti-fouling agent according to this invention. Physical Constants Anti-fouling Performance Test N0, Trialkyl-tin radical Negative substitute radical Rehgdex m, p 1 nth 3 gh 6 01 1,4888 O A 7 oc a 1,4710 A s 0c 11 0c a 1 4718 Q A C2H5 Sn-X Z 4 4 9 9 C H oc n 1,4686 Q Q 2 0130-014 67-69 O A 11 o-co-c n 27-29 Q O a 12 se n 1,4904 0 O 5 13 c1 26. s Q A [:1 14 1z z5 oc n 1,4700 0 A m g CH3 7 OCZH4OC4H9 1,4702 Q Q 5 on 16 3 06121-125 1,4660 Q Q g 17 o-co-c1-1 99-102 Q A o 18 O-CO-C17H35 50 O Q 19 s-c H t; 1,4839 0 O 61 O X s oo e 1,4755 Q X 7 3 oc a oc 11 1. 4688 Q X m g s C I oc a 1,4660 Q A g 9 0 00-01-1 81-82 Q X g 10 O-CO-C17H35 1,4769 0 A m 11 S'CIZHZS 1.4902 O A 12 1143 11 01 1,4890 Q X 13 n-C H Sn-X o-co-c1-1 77-79 Q X 4 9/ A 14 nC4H O-CO-C17H35 37 Q 15 c1 26 Q A 16 o-c n 1,4757 A X -x 3 17 CZH5/Sn oc r1 00 11 1, 4728 A X E c n 3 is Z 5 oc u 1,4710 A X 19 o-co-c1-1 68-72 A X n:

20 o-c0-c n 34-36 A X 21 y 543 11 1,4873 Q A EXAMPLES 20-24 In these Examples, polyethylene fishing nets were coated with an anti-fouling composition comprising the organo-tin compound as the effective substance according to this invention and a base material consisting of ethylene/vinyl acetate copolymer. As the fishing nets, those made of vinylidene chloride/vinyl chloride copolymer (Krehalon, manufactured and sold by Kureha Chemical Industrial Co., Ltd., Tokyo, Japan), were also tested. At the same time, effects of spreaders usable in the invention are also shown.

Table 5 Preferred Com positions No. of Constituents wt. Example parts dimethyl-n-dodecyl tin stearate (mp, C); 3 ethylene wt.%)/vinyl acetate (25 wt.%) copolymer 5 (melt index 150); solvent naphtha 92 dimethyl-mdecyl tin naphthenate; 3 ethylene (72 wt.%)/vinyl acetate (28 wt.%) copolymer I0 21 (melt index l50) (n 1.4938);

solvent naphtha; 87 diethyl-n-octyl tin laurate; 5 ethylene (67 wt.%)/vinyl acetate (33 wt.%) copolymer lo 22 (n IAR'ZO) (melt index 25);

copper naphthcnate (containing 10 wt.% of copper]; 5 solvent naphtha; 8t) tli-n'pmpyl-n-nctyl tin dndecyl ether; 5 23 ethylene ((10 wt/M/vinyl acetate (40 wt.%) copnlymer 5 (n" L 1.4690) (melt index 55). copper nluatc (containing 5 wtfl of copper); 5 solvent naphtha S dimcthyLn-dccyl tin-n -dodecylthiuclhcr;

Preferred Compositions No. of Constituents \vt. Example parts 24 ethylerie (6O wt.7z )/vinyl acetate (40 wtfit copolymer (n= 1.4839) (meltindcx 55); solvent naphtha; -9O nicthylacrylate (60 wt.7r)/tributyl tin aerylate (4t) wtfZ) 10 Ref. copolymer;

22 solvent naphtha; 90 bis-(Tri-n-butyl tintoxide; 50 Ref. copper naphthenate (containing l0 wt.7r of copper); 3O solvent naphtha; 65 tri-n-buiyl tin naphthenate; 5 Ref copper naphthenate (containing l0 wtfil' of copper); 5 24 oil varnish; 90

Table 6 EXAMPLES 25-47 polyethylene nets f adhesion blocking ii i i In these Examples, fishing nets and ropes made of oforgano-tin ol eth lene blended with the or ano-tin anti-foulin P y agent according to this invention were tested. preferred 20 no scale-off non'sticky times exam- 21 do. dov times m gg: In these tests, the organo-tin anti-fouling agent was O. i is, 24 71 times added to pulverized polyethylene (Sholex'6006C) and f y 3 25 dry-blended intimately and the thus compounded mass 22 i f was spun into filaments, 400 denier, by the melt- 4 somewhat spinning process. The spinning unit was of the double 24 Suck) L2 pitch type fitted with a screw, 60 mm diameter. L/D Krehalon nets 22; compression rate 3.0. The orifice plate was Surface formed with 79 extrusion orifices, each bein of 2 mm I adhesw I block l l diameter. The stretch ratio amounted was 10:1; extru- 0 mgmio'im sion rate: 300 g/min; internal temperature, max., preferred 20 no scalc-0ff non- 6.3 times 0 sticky 275 C. The amount of the compound consumed per exam- 2l do. do. 63 times b t h; 59 k ples of 22 do. do. 92 times the in. 23 do. do. 8.3 times vefmion f do. bl n- The physical properties such as tensile strength; elon- .a. un HVOIZI 3 .8 u U sick). gation and knot strength of the filaments when spun ences 23 bad l 4 times from a blended spinning material with the organo-tin \HL' 'y v I Smncwhm anti-fouling agent in the form of tributyl-t1n compound 24 bad sticky L3 times 40 showed somewhat lesser values.

Remarks:

Fishing net was coated with anti-fouling agent. dried under moving atmosphere at room temperature for 24 hours. stuck with an adhesive tape, peeled off and the adhesive conditions of the peeled-off surface ofthe net inspected to determine the adhesive condition thereof.

' Ratio of surface concentration (organoain/devcloper) upon coating and drying] to the concentration of antifouling agent solution (concentration of organo-tin/detelopcr).

Table 7 Results of Anti-Fouling Tests Degree of Deposition of Water Microorganisms after Immersion of testing Materials into the Sea 'Water microorganisms" comprise shellfishes such as harnacle, serpula, poly-tan. mussel, ascidian and the like, and algae such as lavcr, green lover and the like (l 1 l\|t\\tt\l no deposition of water micro-organisms observed,

A \lltil quantity of deposited water microorganisms olncrvcd,

X overall and \lthflttltlltll deposition observed Further, it should be noted that when the blended spinning material with trubutyl-tin compound was spun, an unpleasant and irritating smell resulted. Since tributyl-tin is a highly poisonous substance, the spinning job must be carried out by the hands of operating personnel provided with completely sealed working clothes, resulting in almost impracticability of spinning. On the other hand, with use of the novel organo-tin compounds, the spinning job could be performed with no difficulty.

The aforementioned difficulty by use of tributyl-tin compound or the like can be attributed to the higher vapor pressure of the trialkyl-tin compound than the former.

The filaments blended with the various organo-tin anti-fouling agents were fabricated into ropes, each having a 12 mm O.D., which were then immersed into sea water to test the anti-fouling effect against sea micro-organisms. The results thereof, together with the respective compositions of the blended materials with the organo-tin compounds are shown in the following Table 8.

Table 8 continued n Specification of Mixed Compound gzx iz g i Organic-tin anti-fouling agent H lonol DLTB P after after -1 Chemical Compound and Physical Data I (PHR) (PHR) (Pl-m) Z m nlhi 6 munth m 3 E 3 H CII CHCH O-CO2g-C H g 47 H C-Sn-OI-IC crr-o-m d 2 o 0 l 0 I O 25 12 IZ Z 3 l3 1 o a c -cu n 1 4835) 5 3 & H 3 0 12 n-C H (n 1.4872) 2 5 439 Sn 0 4 0 0.1 O l X 26 n-C4l'l9 Z X 27 n-C4I-l p. 37C) 1 0 0.1 O 1 X n-C H Sn-OuC-C H 2B n-C4H9 o 3 o 0.1 o 1 A x E 3 2 29 n-C4Hg (m.p. za-so'c) Z 0 0.1 0 l X m n-C H Sn-( ocn crr -lo-c H 30 n-C H 4 O 0.1 0 l X Remarkls;

It added weight quantity to 100 weight parts of resin. DEP; diethylphthalate; alpha-MBE, di-alpha-methylbenzylether; raw 0 X 1 overall and substantial t me the case may be.

EXAMPLES 4860 In these tests, fishing nets made of vinylidene chlo ride blended beforehand with the organo-tin compound according to this invention were examined.

The organo-tin anti-fouling agent, together with a proper additive, was added to vinylidene chloride/vinyl chloride copolymer Krehalon resin, manufactured and sold by Kureha Chemical Industrial Co., Ltd, Tokyo, and blended together according to the conventional blending technique. In this way, several batches of compounded masses, each amounting to 50 kg, were prepared. These blended materials were melt-spun under conventionally employed spinning conditions,

: almost no deposition of water micro-organisms observed;

small quantity of deposited water micro-organisms observed;

c q n observed. M The numerical data set forth as A above represent eitherTal-laa index or melting oint, as

into filaments of 1,000 denier. The blending of the organo-tin compound did not adversely affect the desirous physical properties of the filaments as spun, such as tensile strength, elongation, knot strength and loop strength. The bleeding characteristics of the antifouling agent towards the surfaces of the filaments or ropes made therefrom were not adversely affected.

The yarns or ropes made from these filaments were then fabricated into fishing nets which were then immersed into the sea, 1-3 m deep, for testing of the antifouling effect. The results of these tests and the specifications of the compounded materials are given in the following Table 9.

TABLE I Specification of Mixed Compound Anthiouling Performance n: Organo-tin anti-fouling agent alpha barium carbon h DEP MBE atearate black after after Chemical Compound and Physical Data (Pl-LR) (PHR) (PHR) (PHR) (PHR) 2 months 6 months 4s n-C12H C) 1.0 2 3 0.5 0.065 O O 49 cn sn-o-c-c n 1.8 O O 50 on; H v 3. o 0.065 O O 5; 3' 0 11 O O m. 42-52'C WCIOHZK P O O 52 CH Sn O- -C H 2 0 0.065

3 i} 11 35 CH3/ 0 m 54 z 5 17 35 2 0 n n i. O O a c n o g 55 mclzgzs (n 1,4851) L0 n n O A u 56 H; Sn+ocH cH l-o-@-c 1-1 2. 0 ii O O 1 57 CH3 30 4 9 3' 0 n n n n O O a n a (rn.p. 30-365 c g 58 CH $n+OCH CH .)1 5 o fi C 0 n u H n O O U cu; o

59 n-g }?fizi .p. 33-35'(;) 3 O I. II I. I, g sn+ocn cn i o g c n n-C H -P- no C H sn+ocu cri y m .CnHls y n n O 0 C 5 7 '5 J TABLE) (continued) Specification of Mixed Compound Anti-fouling performa ii iz I aw I Organo-tin anti-fouling agent alphabarium carbon 3 It v DE? MBE steal-ate black 2 zz 2 3 2 Chemical Compound and Physical. pm (PI-1R) (PHR) (Pl-LR) (PHR) (PI-1R) 25 n-C H (m.p.37'C) 1.0 2 3 0.5 0,065 X u, 26 n-C H Sn-O-C-C H 2.0 A X u 7 35 g 21 n-C H o 3. 0 A x o n-C H (m.p. 37C) U 2 9\ 0 ll 1| II n X U 29 4 9 f n 55 3. o X m n-C H 6 Remarks:

0 almost no deposition of Water micro-organisms observed;

: overall and substantial deposition observed.

The embodiments ofthe invention in which an exclusive property or privilege is claimed are as follows:

1. An article to be used in or under water and in contact with water, at least the surface of said article being composed of an anti-fouling composition comprising a polymer and an amount of a substance effective to prevent fouling which comprises an organo-tin compound of the formula:

wherein R, is n-dodecyl and R and R are methyl.

2. The article of claim 1 wherein said anti-fouling composition comprises an intimate blend of said polymer and said organo-tin compound.

3. The article of claim 3, wherein said article itself consists essentially of said intimate blend of said polymer and said organo-tin compound.

4. The article of claim 1, wherein said anti-fouling composition is applied to a substrate of a different material.

5. The article of claim 1, wherein said anti-fouling composition is applied to a substrate as a distinct coating.

: small quantity of deposited water micro-organisms observed;

6. The article of claim 1, wnerein tne anti-fouling 20 composition comprises 0.5-200 weight parts of the organo-tin compound per 100 parts of the polymer.

7. The article of claim 3, which is a melt-spun thermoplastic fibrous material containing the organo-tin compound in an amount of 0.5-5 weight parts per 100 parts of the polymer.

8. The article of claim 1, wherein said polymer is a synthetic resin selected from the group consisting ofa polymer of ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl acetate, acrylonitrile, methacrylic acid esters, a polymer of styrene and butadiene, a polyamide, a polyester, a polyurethane, an epoxy and a phenolic.

9. The article of claim 1 wherein the polymer is an ethylene vinyl acetate copolym -and is applied with 35 said orgah'o' iifico'mpoundiii'fhe torm of a solution or dispersion in an organic solvent.

10. The article of claim 1, wherein the polymer is polyester resin oil varnish and is applied with said organo-tin compound in the form of a solution or dispersion in an organic solvent.

11. The article of claim 1, wherein the polymer is vinyl resin varnish and is applied with said organo-tin compound in the form of a solution or dispersion in an organic solvent. 

1.AN ARTICLE TO BE USED IN OR UNDER WATER AND IN CONTACT WITH WATER, AT LEAST THE SURFACE OF SAID ARTICLE BEING COMPOSED OF AN ANTI-FOULING COMPOSITION COMPRISING A POLYMER AND AN AMOUNT OF A SUBSTANCE EFFECTIVE TO PREVENT FOULING WHICH COMPRISES AN ORGANO-TIN COMPOUND OF THE FORMULA:
 2. The article of claim 1 wherein said anti-fouling composition comprises an intimate blend of said polymer and said organo-tin compound.
 3. The article of claim 1, wherein said article itself consists essentially of said intimate blend of said polymer and said organo-tin compound.
 4. The article of claim 1, wherein said anti-fouling composition is applied to a substrate of a different material.
 5. The article of claim 1, wherein said anti-fouling composition is applied to a substrate as a distinct coating.
 6. The article of claim 1, wherein the anti-fouling composition comprises 0.5-200 weight parts of the organo-tin compound per 100 parts of the polymer.
 7. The article of claim 3, which is a melt-spun thermoplastic fibrous material containing the organo-tin compound in an amount of 0.5-5 weight parts per 100 parts of the polymer.
 8. The article of claim 1, wherein said polymer is a synthetic resin selected from the group consisting of a polymer of ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl acetate, acrylonitrile, methacrylic acid esters, a polymer of styrene and butadiene, a polyamide, a polyester, a polyurethane, an epoxy and a phenolic.
 9. The article of claim 1 wherein the polymer is an ethylene vinyl acetate copolymer and is applied with said organo-tin compound in the form of a solution or dispersion in an organic solvent.
 10. The article of claim 1, wherein the polymer is polyester resin oil varnish and is applied with said organo-tin compound in the form of a solution or dispersion in an organic solvent.
 11. The article of claim 1, wherein the polymer is vinyl resin varnish and is applied with said organo-tin compound in the form of a solution or dispersion in an organic solvent. 